Manufacture of higher alcohols by reduction with sodium amalgam



[ -Patentd Nov. 13, 1941 .MANUFACTURE OF HIGHER ALCOHOLS BY REDUCTION WITH SODIUM AMALGAM seamen! Shikata. Nishikn, om, and Yoshiyuki Inoue, Kamikyokn, Kyoto, Japan i I No Drawing. Application December, 1937, Sc-

1181 N0. 180,916. In Jim Flibl'llll'y 15, 1937 1 Claim. (Cl. 260-438) A This invention relates to a manufacturing process of higher alcohols from the corresponding fatty acid derivatives. such as acid chlorides, acid anhydrides and glycerides, comprising continuous treatment of a solution in organic solvents of one of the starting materials with sol am freshly prepared and unaffected by the atmosphere, g

The object of .the invention is to obtains.

process which gives a high yield with the utmost simplicity in which the use of any catalyst, high pressure or a risk of, coloring oi the product may be avoided. I

Up to now 200 atmospheres and an intense I heat 01' 300 C. as well as special catalysts have been necessary for the reduction of higher fatty acids with hydrogen to corresponding alcohols.

In such a process thespecial conditions for reaction should be observed carefully; otherwise, there would oftenbe a danger oi hydrocarbons or. condensation products being produced. As is well known it is theoretically'possible to produce alcohols from fatty acids or their derivatives with metallic sodium or sodium amalgam as a reducing agent. Metallic sodium is however economically unpractical; amalgam can not be used with advantage as a reducing agent or organic compounds on a large production scale as the action of amalgam is restricted to its surface so that the inner portion of mercury is-leit inert.

According to the present invention sodium amalgam obtained by electrolysis or sodium chloride solution with a merairy cathode is immediately led into a reduction chamber and allowed to react with fatty acid derivatives, such as acid chlorides, acid anhydride, and glycerides dissolved in organic solvents under the ordinary pressure and at the room temperature or moderately warmed.

The concentration of the amalgam should be regulated by taking out a minute test-portion and examining the liquidity of the mercury. Mercury is renewed, whenever desirable, while reduction is kept up. The formation or the amalgam is analogous to the manufacturing process or sodium hydroxide and chlorine by electrolysis 0i. sodium chloride solution with the mercury cathode. The advantages or this process are the practicability of economical production of higher alcohols by the use or freshly prepared sodium amalgam.

The following are some practical examples of the process of this invention: g

1. Let us call one of the two neighboring chambers a reduction chamber and the other an" electrolysis chamber. Into the reduction chem} her is introduced a solution of palmitic acid chloride and methanol in the ratio of 30:100v and heated up to C. under a reflux condenser.

Heating may be eflected by sending warm water through a tube which is disposed in the chamber. From the electrolysis chamber sodium amalgam of 0.01%,obtained by electrolysis or sodi'um chloride solution ispumped into the reduction chamber and renewed when required with the aid of a turbine; chlorine produced in the r electrolysis chamber is led into the storage tank by a pipe. The reduction is allowed to go on for about two hours: in the meantime, the percentage of unsaponiflable matter is examined and also its degree of reaction. When the solution is d'rivenout of the-reduction chamber a new acid chloride solution run in and treated in the same manner. 'I'hesolution i'rom the reduction chamber is distilled for the recovery or the solvent and the residue is mixed with a large quantity of a warm alkaline solution, agitated and cooled; the semi-solid matter which sathers in the upper layer is collected and distilled oi! as palmitic alcohol by the ordinary process.

2. Into the, reduction chamber is introduced a mixture or lauric acid anhydride, toluenesaturated with water and phosphoric acid in, the ratio or 20:100z5 and treated as in the previous example. To the solution which has run out of the reduction chamber is added a large quantity or water so as to form two layers. .By distilling separately the layer of toluene. lauryl-alcohol is obtained. v 3. The reduction-chamber is ruled with a mixture' of coconut oil,.methanol and glacial acetic acid ,in the ratio 01' 20 :3, reduced and distilled as in the preceding example when coconut oil alcohol is obtained. V v y 4. .5 parts or sodium bisulphate are suspended "in 2 parts of hydrogenated-soya-bean oil heated up to the melting point (sometimes a small quantity of water is to be added) and'treated'asin the former example. From time to time a minute test-portion is'taken out and the reduction is examinedby heating with sodium hydroxide solution. until it shows no sign or practically no a sign or saponiflcation. 'I'hereupon, a greater part of the solutionis run out and a new hydrogenated soya-be'an oil and sodium bisulphate is added while electrolysis and renewal of mercury in the other chamber is beihgconstantly continued. The warm solution removed Irom'the chamber is filtered oil from inorganic salts and V allowed to coolto deposit higher alcohols from I 2 mes es which glycerine is separated by means of vacuum filtering or vacuum fractional distillation. In

this process the solutionin the reduction cham ber becomes neutral. What we claim is:

A process of manufacturing higher alcohols 1mm a corresponding fatty'acid deriyative of the class consisting oi, acid chlorides, acid anhydrides and glycerides comprising continuously treating a solution in an organic solvent of the starting material with freshly prepared sodium 5 amalgam, unaflected by the atmosphere.

SEISHICHI SHIKATA. YOSHIYUH INOUE. 

